Vat dyestuffs of the anthraquinone series



Patented Oct. 10, 1939 UNITED STATES PATENT OFFICE VAT DYESTUFFS OF THE ANTHBAQUINONE SERIES Ernst Honold and Max Schubert, Frankfort-onthe-Main-Fechenheim, Germany, assignors to General Aniline Works, Inc, New York, N. Y.,

a. corporation of Delaware No Drawing.

Application May, 1938, Serial No. 209,726. In Germany May 29, 1937 4 Claims.

wherein R stands for a member of the group consisting of hydrogen and halogen, n and in stand for one of the numbers 1 and 2, Y for a member of the group consisting of S- O and 20 X for a member of the group consisting of the phenylene, halogenated phenylene, alkoxyphenylene, the naphthalene, the diphenylene radical, the radical of diphenyleneoxide, fluorene, carbazole and diphenylsulilde, and an ar-aliphatic 25 radical (ar meaning the phenyl radical), A stands for a member of the group consisting of -N=N--,

X1 meaning a member of the group consisting of the diphenylene, azobenzene and benzophenone radical, the pairs of X, Y, n and m having identical value.

40 The new vat dyestuffs are obtainable by condensing such amines of the anthraqulnone series as contain in ortho-position to the amino group a further amino group or a hydroxy or mercapto group, which amines are able to form an imid- 45 azole or oxazole or thiazole ring during the condensation reaction, with carboxylic acids of the general formula:

wherein n, m, X, A and X have the above said signification, or their functional derivatives.

Advantageously the condensation reaction is performed in organic solvents. By acting with 55 the carboxylic acid chlorides of the said azo or (Cl; Milk-157) azoxy compounds on the amines condensation ocurs in some cases already at room temperature. The condensation reaction is finished at elevated temperatures whereby simultaneously the formation of the azole ring is performed.

The some new condensation products can be obtained by starting from such amines of vattable ring systems, as contain in o-position to the amine group another suitable substituent such as for example a halogen atom, which substituent can be replaced by (or converted to) an amlnouor hydroxy or mercapto group, after the condensation of the amine with the carboxylic acid has been performed. Hereafter the formation of the azole ring is carried out.

The present new dyestuffs are moreover partly obtainable by starting from compounds of the general formula:

wherein Y has the above signification and Z stands for a nitrogenous group of a lower or higher degree of oxidation than an azoor azoxyroup. If Z stands for a group of a lower degree of oxidation, the present dyestuffs are obtainable by oxidation according to usual methods of such initial products, if Z stands for a group of a higher degree of oxidation, then reduction of such initial products yields the present new dyestuffs.

The present new dyestuffs thus obtained dye vegetable fibers from the vat yellowish shades and exhibit a good iastness to chlorine and boiling soap solution and in many cases to light. It is a surprising fact that the new dyestuffs are likewise vattable compounds and that the azo or azoxy groups contained in these compounds are not reduced in the vat with splitting of the molecule and formation of amines.

In order to further illustrate our invention the following examples are given, the parts being by weight and all temperatures in degrees centigrade.

Example 1 dissolves in concentrated sulfuric acid with red color and dyes cotton from a violetish red vat very fast yellow shades.

When using as one reaction component the 3.3 dimethoxyazobenzene 4.4 dicarboxylic acid dichloride or the azoxybenzene-4.4-dlcar boxylic acid dichloride very similar vat dyestuffs are obtained.

Example 2 To a suspension of 28 parts of the sodium salt of 2-amino-l-mercaptoanthraqulnone in about 300 parts of nitrobenzene 16 parts of a20- benzene-3.3-dicarboxylic acid dichloride are added. The mixture is stirred at room temperature for about 3 hours and then boiled for about 8 hours in an apparatus provided with a reflux condenser. While hot the condensation product from a violetish red vat strong greenish yellow shades of good fastness properties.

A very similar dyestuff is obtained when using as one reaction component the 4.4-dichloroazobenZene-3.3'-dicarboxylic acid dichloride.

Example 3 To a suspension of 25 parts of 3'-aminophenyl 1-(S) -2(N) -thiazolanthraquinone of the forin about 500 parts of water a mixture of 100 parts of an aqueous sodium carbonate solution of 10% strength and of about 500 parts of a sodium hypochlorite solution containing about 12 to 15% of active chlorine is added. Then the mixture is held, while stirring, at to until the coloration has turned to yellow orange and unchanged amine can no more be detected. The formed reaction product is filtered off, washed out and dried. It is identical to the condensation product of Example 2, paragraph 1.

Example 4 According to the process as described in Example 2, 28 parts of the sodium salt of 2-amino-l-mercaptoanthraquinone are condensed with 23 parts of diphenylazodiphenyl-4A'-dicarboxylic acid dichloride in the presence of nitrobenzene. The formed dyestufl of the formula:

0 HEQOQGOF 0 thus formed is isolated and may be purified by treatment with a hypochlorite solution. The new dyestufi of the formula:

dissolves in concentrated sulfuric acid with a slightly yellowish brown color and dyes cotton dissolves in concentrated sulfuric acid with a violetish red color and dyes cotton from a violetish red vat very fast yellow shades.

When condensing according to the same process the sodium salt of 2-amino-1-mercaptoanthraquinone with azobenzene-4,3,5'-tricarboxylic acid trichloride there is formed a condensation product of the formula:

When using as second reaction component azobenzene-3,5,3',5'-tetracarboxylic acid tetrachloride the condensation product corresponds with the forumla:

When using diphenyleneoxide-azo-diphenyleneoxide-2.2-dicarboxylic acid dichloride the condensation product corresponds with the formula:

In the same manner, one may condense the the fluorene, carbazole and diphenyisulflde series,

while forming the corresponding condensation products.

When condensing in the same manner the sodium salt of 2-amino-1-mercaptoanthraquinone with 1.1-azonaphthalene-5.5'-dicarboxy1ic acid dichloride the condensation product corresponds with the formula:

When using as second reaction components 3.3- azocinnamic acid dichloride, 4.4'-azophenoxyacetic acid dichloride and 4.4-azophenylacetic corresponding diearboxylic acid dichlorides of acid dichloride the formed condensation products 75 correspond with the following formulae respecobtainable by condensing one molecular proportivelyz tion of 4.4'-diaminoazobenzene with two mo1ecm 11 HC H and ular proportions of the methylester of 4-nitroso- When using as second reaction component the benzoic acid, saponifying the condensation proddichloride of the formula:

uct formed and treating it with phosphorus pentachloride the formed condensation product corresponds with the formula:

obtainable by condensing one molecular proportion of benzidine with two molecular proportions of the methylester of 4-nitrosobenzoic acid,

When condensing in the same manner one molecular proportion of 4.4-diaminobenzophenone and of 4.4'4"-triaminotriphenylmethane with two and three molecular proportions respecsaponifying the formed condensation product and treating it with phosphorus pentachloride, the formed condensation product corresponds with the formula:

tively of the methylester of 4-nitrosobenzoic acid,

When using as second reaction component the saponifying the formed condensation products dichloride of the formula:

and treating them with phosphorus pentachloride and finally condensing the chlorides thus formed with the sodium salt of Z-amino-l-mercaptoanthraquinone the formed condensation products correspond with the formulae:

ponent, the formed dyestufl dyes cotton fast yellow shades of a somewhat more greenish tint.

A very similar dyestufi is obtained when using as one reaction component the diphenyl-azoxydiphenyl-4.4'-dlcarboxylic acid dichloride.

/ON=N.O I QS o All of these condensation products dissolve in concentrated sulfuric acid with a yellowish-brown to dark red color and'dye from a brown to a violet vat the vegetable fibers, fast yellow shades.

Example 5 To a solution held at about 160 of 24 parts of 1-amino-2-hydroxyanthraquinone in about 300 parts of nitrobenzene, 16 parts of azobenzene- 4.4'-dicarboxylic acid dichloride are added and the mixture is boiled for about 8 hours in an apparatus provided with a reflux condenser. The condensation product, which separates almost completely in the heat, is isolated. The new dyestufi of the formula:

o N=ZEON= dissolves in concentrated sulfuric acid with,a orange red color and dyes cotton from a dark red vat fast somewhat greenish yellow shades. The dyestufi is very fast to chlorine and may be purified, if necessary, by treatment with a chlorinating agent.

When using diphenyl-azodiphenyl-4.4'-dicarboxylic acid dichloride as second reaction com- To a suspension of 23 parts of 4-aminophenyl- 2,1-(N)-oxazoloanthraquinone of the formula:

0 HIGH.

in about 500 parts of water, 100 parts of an aqueous sodium carbonate solution of 10% strength and about 500 parts of a sodium hypochlorite solution containing 12 to 15% of active chlorine are added. Then the mixture is stirred at to until the color has turned to yellowish orange and no more unchanged amine can be detected. The formed reaction product is isolated and dried. It is identical with the dyestufl as described in paragraph 1 of the foregoing example.

Example 7 To a solution of 34 parts of l-methylamino-Z- amino-3-brom-anthraquinone in about 300 parts 5 of trichlorobenzene, while stirring, at about 160,

wherein R stands for a member of the group con- N 5 16 parts of azobenzene-4.4'-dicarboxylic acid dichloride are added and the mixture is boiled for x for a member of the group consisting f the about 8 hours in an apparatus provided with a rephenylene, halogenated phenylene, alk0xyphe flux c nd rh on n p u whi h ylene, the naphthalene, the diphenylene radical, 10 ep t 1n the t filtered off, washed ut the radical of diphenyleneoxide, fiuorene, car- 10 and driede ew ye t fi 0 the formula! bazole and diphenylsulfide, and an ar-aliphatic CH: (IJH: O Q

B B r g0 dissolves in concentrated sulfuric acid with a radical (ar meaning the phenylradical),Astands yellow color and dyes cotton from a red vat fast for a member of the group consisting of 55 yellow shades. -N=N-, A very similar dyestuff is obtained when using =N as second reaction component azobenzene-3.3'- H dicarbox lic acid dichloride. -N=N-Xi--N=N and so Example 8 N=NX;-N=N 14 parts of the sodium salt of l-amino-Z-mer- II I; captoanthraquinone are condensed with 8 parts of azobenzene-4A-dicarboxylic acid dichloride X meaning a member of the group Consisting of y e n for some hOIlrS With the a o of the diphenylene, azobenzene and benzophenone nitrobenzene at about 220. The condensation i l, th pairs of X, Y, n and 111 having idemproduct of the formula: tical value, which dyestuffs dye vegetable fibers 0 N=IQN= o 40 is isolated. It dissolves in concentrated sulfuric from the vat yellowish shades and exhibit a good acid with an orange-red color and dyes cotton fastness to chlorine and boiling soap solutions. 50 from a dark red vat fast greenish yellow shades. 2. A vat dyestuff of the anthraquinone series We claim: of the formula:

O Q C l L N 60 60 1. Vet dyestufi's of the anthraquinone series corresponding to the formula:

which dyestufi dissolves in concentrated sulfuric acid with a red color and dyes cotton from a vio- II N from a violetish red vat very fast yellow shades. 4. A vat dyestufi of the anthraquinone series which dyestuff dissolves in concentrated sulfuric 3. A vat dyestufi of the anthraquinone series of the formula:

which dyestuft dissolves in concentrated sulfuric acid with a violetish red color and dyes cotton ERNST HONOLD. MAX SCHUBERT.

acid with a brown color and dyes cotton from a. reddish brown vat fast yellow shades. 

